The present invention relates to a process for preparing diacetals of glyoxal by reacting from 40 to 75% by weight aqueous glyoxal with monohydric alcohols in the presence of an acid catalyst.
Diacetals of glyoxal, which are sometimes also referred to as tetraacetals, are interesting precursors for organic synthesis. The most important preparative method for diacetals of glyoxal is the acid-catalyzed acetalization of glyoxal using monohydric alcohols Rxe2x80x94OH according to the following scheme: 
The acid-catalyzed acetalization of glyoxal using monohydric alcohols is a complex reaction which, in addition to the monoacetal and diacetal, may also form a multitude of oligomers and/or cyclic by-products (see, for example, J. M. Kliegmann et al. in J. Org. Chem. Vol. 38 (1973) p. 556; J. Org. Chem. Vol. 37 (1972) p. 1276ff; A. Stambouli et al., Bull. Soc. Chimique France (1983) II p. 33-40.
U.S. Pat. No. 2,360,959 describes the preparation of diacetals of glyoxal from alcohols which are water-immiscible. To this end, aqueous glyoxal and a small quantity of acid catalyst are heated with at least 4 mol of the water-immiscible monohydric alcohol, an azeotropic mixture of water and alcohol is distilled off and the alcohol, after removal of the water, is recycled to the reaction. The reaction of glyoxal with methanol likewise described there is carried out in a similar way, although to separate water from alcohol, an additional, complicated fractional distillation has to be carried out. In the case of water-miscible alkanols such as methanol or ethanol, however, this process only delivers the corresponding 1,1,2,2-tetraalkoxyethane in low yields (38% in the case tetramethoxyethane).
GB 559,362 recommended the use of a water-immiscible, liquid, inert solvent such as benzene, toluene, xylene, hexane, dichloroethane or isopropyl ether in the acid catalyzed acetalization of glyoxal with monohydric alcohols. However, the use of azeotroping agents leads to additional process costs. Also, at least the halogenated azeotroping agents are toxicologically or ecologically unsafe.
F. H. Sangsari et al., Synth. Commun. 18(12) (1988) p. 1343-1348 recommended acetalization in the presence of an azeotroping agent such as chloroform using a Soxhlett apparatus filled with a drying agent to remove the water of reaction formed in preparing 1,1,2,2-tetramethoxyethane and 1,1,2,2-tetraethoxyethane.
The prior art processes for preparing diacetals of glyoxal have the disadvantage that when water-miscible alcohols such as methanol or ethanol are used, the yield of diacetal, i.e. of 1,1,2,2-tetraalkoxyethane, is low. Also, all processes require distillative measures during the conversion to remove the water of reaction which leads to increased energy and equipment costs and complicates the continuous operation of the reaction. The use of an azeotroping agent to remove the water of reaction in turn has the disadvantage that the concomitantly distilled alcohol and the azeotroping agent have to be separated.
It is an object of the present invention to provide a process for preparing diacetals of glyoxal which, even when water-miscible alcohols are used, delivers the appropriate diacetal in good yields and may be made continuous in a simple manner.
We have found that, surprisingly, this object is achieved by a process which comprises contacting a liquid mixture which, at the beginning of the reaction, comprises alcohol and glyoxal in a molar ratio of at least 15:1 and also water in a concentration of not more than 8% by weight with an acid catalyst until an approximate reaction equilibrium has been attained. According to the invention, it is believed that at least approximate reaction equilibrium has been attained when the concentration in the reaction mixture of the diacetal formed is at least 70% of the equilibrium concentration of diacetal applying to the particular composition.
Accordingly, the present invention relates to a process for preparing diacetals of glyoxal by reacting from 40 to 75% by weight aqueous glyoxal with monohydric alcohols in the presence of an acid catalyst, which comprises contacting a liquid mixture which, at the beginning of the reaction, comprises alcohol and glyoxal in a molar ratio of at least 15:1 and also water in a concentration of not more than 8% by weight with the acid catalyst until concentration in the reaction mixture of the diacetal formed reaches at least 70%, preferably at least 80%, in particular at least 90% and more preferably at least 95%, of the equilibrium concentration without more than 5% by weight of the alcohol used having already been distilled off.
The water concentration in the liquid mixture at the beginning of the reaction is preferably in the range from 2 to 8% by weight and in particular is not more than 7% by weight, for example from 3 to 7% by weight, and more preferably not more than 6% by weight, for example from 3 to 6% by weight, based in each case on the total weight of the liquid mixture. The total weight of the liquid mixture is calculated from the sum of all liquid components contained in the mixture and components dissolved therein. It does not include components which are not dissolved in the mixture such as heterogeneous catalysts. In principle, the water concentration may be adjusted in different ways:
a) for example, glyoxal can be used which has a content of at least 50% by weight and preferably at least 60% by weight. The glyoxal content of the aqueous glyoxal solution will preferably not exceed a value of 75% by weight.
b) a second possibility is to use a large excess of alcohol, for example, more than 30 mol of alcohol per mole of glyoxal, for example, from 30 to 50 mol of alcohol/mol of glyoxal in the liquid mixture.
c) a third possibility for adjusting the water content at the beginning of the reaction is adding an inert substance to the liquid mixture which is completely soluble in and/or completely miscible with the liquid mixture. When an inert substance is used, it is generally used in a quantity of at least 1% by weight, for example from 1 to 25% by weight, preferably from 2 to 20% by weight.
Preference is given to the measures a) and c), in particular a). It will be appreciated that the abovementioned measures may also be combined with each other, preferably measure a) with measure b) or measure a) with measure c).
In principle, inert substances include aprotic organic solvents and also neutral or weakly acidic salts which do not catalyze the acetalization. Preference is given to neutral or slightly acidic salts. Examples of useful salts include the halides, sulfates, nitrates, monoalkylsulfates, arylsulfonates and alkylsulfonates of metals of the first and second main group, for example, of Na, K, Li or Mg, of quaternary ammonium cations and also of iron(II) and iron(III) ions. Preferred salts include the sulfates, monoalkylsulfates, arylsulfonates and alkylsulfonates of the metals mentioned or of quaternary ammonium cations. A particular example of an alkylsulfate is methylsulfate. Particular examples of arylsulfonates include the phenylsulfonates and the tolylsulfonates. An example of an alkylsulfonate is methylsulfonate.
Examples of quaternary ammonium cations include the tetrakis-C1-C10-alkylammonium cations such as methyltriethylammonium and methyltributylammonium and also the phenyl- and benzyl-tris-C1-C4-alkylammonium cations such as benzyltrimethylammonium or benzyltriethylammonium.
Examples of useful salts which are sufficiently soluble in the liquid mixture and are inert under the reaction conditions, i.e. do not catalyze the acetalization, include in particular the tetrakis-C1-C10-alkylammonium alkylsulfates such as methyltriethylammonium methylsulfate and methyltributylammonium methylsulfate.
When a heterogeneous acetalization catalyst is used, in particular a strongly acidic ion exchange resin, the reaction mixture customarily contains no inert salt.
When aqueous glyoxal having a glyoxal content of at least 50% by weight and preferably at least 60 to 75% by weight is used in the process according to the invention, this is prepared by concentrating commercial aqueous glyoxal, which customarily has a glyoxal content of about 40% by weight, under reduced pressure. The aqueous glyoxal is preferably concentrated immediately before use, i.e. the concentrated aqueous glyoxal is not stored for more than 5 h, preferably not more than 2 h and in particular not more than 30 min before it is used. Concentration is preferably effected at a pressure below 500 mbar, for example from 10 to 500 mbar, preferably below 300 mbar and in particular in the range from 50 to 300 mbar. Preference is given to concentrating the aqueous glyoxal at temperatures in the range from 40 to 100xc2x0 C., depending on the desired pressure and the type of vaporizer.
Preference is given to using apparatus to concentrate the aqueous glyoxal which allows a very gentle concentration process, i.e. that subject the distillation residue to very little thermal stress during concentration. In principle, useful apparatus includes that which is based on the vaporization of thin films, i.e. thin film evaporators such as falling film evaporators, blast pipe evaporators, rotary thin film evaporators, e.g. Sambay evaporators or Luwa filmtruders, and also centrifugal evaporators. Circulation evaporators such as, in particular, forced circulation evaporators, forced circulation depressurization evaporators, and also natural circulation evaporators are also suitable. Useful evaporator designs include both tube and plate apparatus. Such evaporators are well known to those skilled in the art and described, for example, in R. K. Shah and A. C. Mueller, xe2x80x9cHeat Exchangexe2x80x9d chapter 2.2.2.1, Ullmann""s Encyclopedia of Industrial Chemistry, 6th ed. on CD-ROM, Wiley VCH.
In particular, multistage designs of the abovementioned evaporators are suitable. They may combine either identical or else different evaporators. For example, a circulation evaporator may first be used to remove a portion of the water and then a thin film evaporator may be used to adjust the desired glyoxal content. When the stages are operated at different pressure levels, the thermal energy of the vapor from the higher pressure stage may be utilized for vaporization in the lower pressure stage.
To concentrate the aqueous glyoxal, multistage separating apparatus such as countercurrent distillation columns having internals may also be used. A portion of the water may also be removed in apparatus for evaporating liquids, for example, Venturi or spray apparatus or falling film apparatus, which may be operated in cocurrent or countercurrent.
The vapors which comprise water and glyoxal traces will frequently be condensed in a condenser. What is known as vapor compression (thermal compression) by means of a vapor compressor may also be employed to utilize a portion of the thermal energy of the vapors to heat the aqueous glyoxal and at the same time to condense the water.
Stripping columns are also suitable, for example those having internals, for example, random packing, structured packing or tray columns, or those without internals, what are known as spray columns. When these types are used, concentration will be effected by introducing optionally prewarmed aqueous glyoxal at the top of this apparatus and passing in the stripping gas, preferably an inert gas, which is preferably also prewarmed, into the lower section of the column. The concentrated aqueous glyoxal solution is obtained at the bottom of the stripping column, while the water-enriched stripping gas leaves from the upper section of the apparatus. In a closed system, the moisture loading of the stripping gas can be reduced by cooling in a condenser, reheating the dried gas and passing it back into the stripping column.
In principle, all available monohydric alcohols may be used in the process according to the invention. Preference is given to alcohols whose OH group is located on a primary or secondary, preferably primary aliphatic carbon atom. Examples thereof include C1-C10-alkanols such as methanol, ethanol, n- or iso-propanol, n-, iso- or sec-butanol, n-hexanol, n-octanol, 2-ethylhexan-1-ol, C5-C10-cycloalkanols such as cyclopentanol or cyclohexanol, allylic alkanols such as allyl alcohol, arylalkanols such as phenylethanol or benzyl alcohol.
According to the invention, preference is given to the water-miscible alcohols such as methanol, ethanol, n- and isopropanol. The preparation of 1,1,2,2-tetramethoxyethane by acetalizing glyoxal with methanol is a particularly preferred embodiment of the process according to the invention.
According to the invention, the molar ratio of alcohol to glyoxal is at least 15:1 and is preferably in the range from 15:1 to 50:1 and in particular in the range from 18:1 to 30:1. Higher alcohol fractions are possible (see above), but generally require more processing.
Useful acid catalysts include both Lewis and Brxc3x6nstedt acids, which, as will be known, can be used for acetalizing aldehydes. The catalysts used may be those which dissolve homogeneously in the mixture or else heterogeneous catalysts. Examples of homogeneous catalysts include, in particular, sulfuric acids and also organic sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid or sulfuric monoesters. Trichloroacetic acid or oxalic acid may likewise be used. Examples of useful heterogeneous catalysts include zirconium sulfate and also strongly acidic, in particular sulfonic acid, ion exchangers. Examples of useful acidic ion exchangers, which are used in particular in macroporous form, include ion exchangers which are sold under the brand names Lewatit(copyright), BayKat(copyright) (Bayer AG, Leverkusen), Amberlite(copyright) and Amberlyst(copyright) (Rohm and Haas) and also Dowex(copyright) (Dow Chemicals). Examples of commercially available strongly acidic ion exchangers in macroporous form include Lewatit(copyright)S 100, Lewatit(copyright)K 2431, Lewatit(copyright)K 2621, Lewatit(copyright)K 2629, BayKat(copyright)K 2611, Amberlyst(copyright)15, Amberlyst(copyright)35 and also Dowex(copyright)50. The quantity of acid catalyst in homogeneous catalysis is generally at least 0.5% by weight, preferably at least 1% by weight and, when a heterogeneous catalyst is used, generally at least 5% by weight, in particular at least 10% by weight, based in each case on the total weight of the liquid mixture. Higher catalyst quantities are generally not disadvantageous. Particularly in heterogeneous catalysis, the catalyst quantity is limited only by the liquid volume, and the maximum catalyst quantity corresponds to a fixed catalyst bed.
In a preferred embodiment of the process according to the invention, a heterogeneous catalyst is used in the form of a fixed bed, through which the liquid mixture comprising alcohol and aqueous glyoxal is passed. The liquid mixture may be passed more than once through the fixed bed until the desired contact or residence time is attained. However, the liquid is preferably passed through the catalyst bed only once, i.e. in straight pass.
The temperatures required for acetalization are generally above room temperature and are preferably at least 50xc2x0 C. and in particular are in the range from 50 to 80xc2x0 C. and more preferably in the range from 65 to 75xc2x0 C. The discontinuous method offers the particular possibility of working at the boiling temperature of the reaction mixture. The process according to the invention may be carried out at atmospheric pressure, at reduced or else at elevated pressure. Preference is given to carrying out the process at atmospheric pressure or at an elevated pressure of up to 5 bar.
In the process according to the invention, the reaction of glyoxal with the alcohol is carried on at least until approximate attainment of the state of equilibrium, i.e. until the concentration of the diacetal in the reaction mixture is at least 70%, preferably at least 80%, in particular at least 90% and more preferably at least 95% of the equilibrium concentration value. The time taken for the acetalization equilibrium to be attained can be quickly determined in a preceding experiment using reaction kinetics. In general, it is at least 2 and preferably at least 3 hours under the reaction conditions stated above. Frequently, equilibrium has been attained after just 10 hours. It will be appreciated that longer reaction times, e.g. up to 36 hours and preferably up to 24 hours, are also possible. Preference is given to a reaction time of from 3 to 8 hours.
After the reaction equilibrium has been attained, the acid catalyst in the case of homogeneous catalysis is deactivated in the reaction mixture by neutralizing with a suitable base such as alkali metal hydroxides or alkaline earth metal hydroxides such as NaOH, KOH or Ca(OH)2, preferably neutralizing with alkali metal carbonates such as sodium carbonate or potassium carbonate or with alkali metal hydrogen carbonates such as sodium hydrogen carbonate or potassium hydrogen carbonate. In the case of heterogeneous catalysis, the catalyst is separated from the reaction mixture, for example, by filtration or, when a fixed bed catalyst is used, by decoupling the material stream from the catalyst bed.
After deactivation or removal of the acid catalyst, the liquid mixture obtained is distillatively worked up in a customary manner. In general, the excess alcohol is first distillatively removed. The alcohol distilled off is preferably reused in the next reaction batch or, in the continuous method, reintroduced to the reactor. In principle, the diacetal may be recovered and removed from coproduced monoacetal and any higher molecular weight by-products by the method described in DE-A 196 51 325. This generally involves redistilling the distillation residue remaining after distillative removal of the alcohol with the addition of water, which distills off the desired glyoxal diacetal and a large part of the water as a homoazeotrope. It has proven useful to use a portion of the water added in the form of the condensate recovered when concentrating the aqueous glyoxal, since the glyoxal contained in the condensate may be recovered in this way. The quantity of water added is preferably determined so that the total quantity of water added and the water already present in the reaction mixture exactly corresponds to the water quantity which is required for the water/glyoxal diacetal homoazeotrope. The quantity required may easily be determined by those skilled in the art using the concentrations of glyoxal and water in the reaction mixture. The distillation residue which substantially comprises the monoacetal and unconverted glyoxal, any residues of diacetal, small quantities of water and any higher oligomeric by-products may, after dewatering if necessary, likewise be recycled to the reaction.
The glyoxal diacetal may be recovered by dewatering water/glyoxal diacetal homoazeotrope resulting from the distillation in a customary manner, for example, by azeotropic distillation in the presence of the abovementioned azeotroping agents, in particular hexane, cyclohexane, heptane, octane, toluene or xylene. This procedure has the particular advantage that a complicated removal of alcohol and azeotroping agent, which is necessary in the prior art processes, is avoided.
In a preferred embodiment of the present invention, the reaction of glyoxal with the monohydric alcohol is carried out continuously using a heterogeneous, strongly acidic catalyst. This generally involves continually feeding a liquid mixture which comprises aqueous glyoxal and the monohydric alcohol and also not more than 8% by weight, preferably from 2 to 8% by weight and in particular from 3 to 7% by weight of water, into a reactor which contains a heterogeneous acid catalyst, and continuously withdrawing a liquid reaction mixture from the reactor. According to the invention, the residence time in the reactor is chosen in such a way that the concentration of the diacetal in the discharged liquid reaction mixture is at least 70%, preferably at least 80%, in particular at least 90% and more preferably at least 95% of the equilibrium concentration.
The average residence time of the reaction mixture in the reactor under the above reaction conditions is generally in the range from 2 hours to 10 hours and preferably in the range from 3 hours to 8 hours.
In principle, the remarks made above apply to the type of catalyst, the pressure and the temperature. However, preference is given to working at slightly above atmospheric pressure, e.g. from 1.1 to 5 bar. The liquid reactor effluent may likewise be worked up in the above manner.
The process according to the invention may be carried out continuously in reactors customary for continuous reaction of liquids over heterogeneous catalysts, for example in continuous stirred tank, columns or preferably in reactors having tubular geometry (tubular reactors). Preference is given to those reactors in which the heterogeneous catalyst is disposed in the form of one or more fixed beds. These include tubular reactors and columns.
According to the invention, preference is given to tubular reactors, since the acetalization equilibrium is attained particularly rapidly. Here and hereinbelow, tubular reactors include both shaft reactors (individual reaction tubes) and also tube bundle apparatus. The tubular reactors may be disposed horizontally but are preferably disposed vertically. When disposed vertically, the liquid reaction mixture may be passed either upward or else downward through the reactor.
In the tubular reactors, the heterogeneous catalyst is generally arranged in the form of one or more beds, and the reactors are generally equipped with devices which substantially prevent discharge of the catalyst during operation. The use of more than one different catalyst in structured beds is also possible.
The tubular reactors may also be equipped with internals at one or more locations through which heat may be introduced or removed. Examples of such internals include coiled tubes and horizontally or vertically disposed tubes or plates. These internals may conduct liquid or vaporous heat carriers in a controlled manner. Condensation and evaporation procedures in the reactor may also be utilized in a known manner to introduce or remove heat.
In the continuous embodiment of the process according to the invention, it has proven to be useful not to add the alcohol and aqueous glyoxal in separate streams but instead to feed the above-described liquid mixture into the reactor. The liquid mixture may, for example, be prepared in a reservoir by mixing aqueous glyoxal of the desired concentration and the alcohol and also any recycled alcohol and any recycled acetal and then the mixture obtained passed into the reactor. However, the individual material streams may be passed in succession or simultaneously through devices for mixing liquids and fed into the reactor. In principle, all known devices for continuously mixing liquids such as jet mixers, static mixers and dynamic mixers are suitable. Examples of such mixers are known to those skilled in the art, for example from H. J. Hensler, xe2x80x9cContinuous Mixing of Fluidsxe2x80x9d in Ullmann""s Encyclopedia of Industrial Chemistry, 5th ed. on CD-Rom, Wiley-VCH, Weinheim.
In a preferred embodiment of the continuous process, 60 to 75% by weight aqueous glyoxal is first prepared in the manner described above by concentrating a conventional aqueous glyoxal solution under reduced pressure and then immediately transferred into the reactor with the alcohol, which comprises both fresh alcohol and any recycled alcohol, and together with any recycled mono- and any diacetal.
It has also proven useful to recycle the alcohol removed in the workup back into the reaction, so that at least a portion of the alcohol in the mixture which is fed into the reactor results from the recycled alcohol. This may result in the mixture fed into the reactor comprising small fractions of mono- and diacetal. It is also possible to recycle the higher-boiling fractions resulting from the workup which, as well as the glyoxal monoacetal, may also contain residues of glyoxal diacetal and higher-boiling oligomers back into the continuous reaction, for example, together with the recycled alcohol. It will be appreciated that the streams are chosen in such a way that the desired alcohol/glyoxal ratio and the water content are in the ranges according to the invention.
The process according to the invention delivers the diacetals of glyoxal in high yields. Surprisingly, distilling off the water formed in the reaction is not necessary to obtain the high yields. The process according to the invention may accordingly be operated continuously in a simple manner. Separation of water and alcohol during the reaction, which would make high demands on both energy and apparatus, is not necessary.
The invention is illustrated by the following examples: